JP2879142B2 - Method for producing metal heat mode recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to an improved heat mode recording material containing a thin metal recording layer.

BACKGROUND OF THE INVENTION Recording materials have been published in which recordings are made thermally by the use of intense radiation, such as a laser beam having a high energy density. In such thermal recording or heat mode recording materials, information is recorded by creating a difference in reflection and / or transmission optical density on the recording layer. The recording layer has a high optical density and absorbs a radiation beam impinging thereon. The conversion of radiation to heat results in a local temperature rise, causing thermal changes such as evaporation or ablation in the recording layer. As a result, the illuminated portions of the recording layer are wholly or partially removed, forming a difference in optical density between the illuminated and non-illuminated portions (US Pat. No. 4,216,501, 42).
33326, 4188214 and 4291119, and British Patent 2026346).

[0003] The recording layer of such a heat mode recording material,
Usually made from metals, dyes, or polymers. Such recording materials are available in The Proceedings of the Eleventh S
E by ML Levene et al. at ymposium (1969)
lectron, Ion and LaserBeam Technology; Elec
tronics (March 18, 1968) at page 50; The B
ell System Technical Journal Vol. 50 (197
1) by D. Maydan at 1761; and Science V
ol. 154 (1966) p. 1550, CO Carlson
It has been announced by.

[0004] Recording on such a thermal recording material is usually achieved by converting the information to be recorded into an electrical time series signal and scanning the recording material with a laser beam modulated according to the signal. This method is advantageous in that the recorded image can be obtained in real time (ie, instantaneously). This type of recording material is referred to as a direct read after write (DRAW) material. DRAW recording materials can be used as a medium for recording an imagewise modulated laser beam to create a human readable or machine readable record. A human readable record is, for example, a microimage that can be read when enlarged and projected. The machine readable DRAW recording material is an optical disc. Until now, tellurium and its alloys have been the most widely used for the production of optical discs, forming highly reflective thin metal films, where heating with a local laser beam is reflected by pit formation. Reduce performance (eg periodicals Physik in unserer Zei
t'15, 1984 Nr. 5 pages 129-130 Jo
See chen Fricke's paper Optische Datenspeicher). Tellurium is toxic and has poor archival properties due to its sensitivity to oxygen and humidity. Other metals suitable for use in DRAW heat mode recording are US-P 4,499,178 and US-P 438.
8400. To avoid toxicity problems, other relatively low melting metals such as bismuth have been introduced in the production of heat mode recording layers. By exposing such a recording material with a pulse of a high-power laser for a very short time,
Radiation is converted to heat when it strikes the bismuth layer. As a result, the writing spot ablates or melts a small amount of the bismuth layer. When melted, the layer shrinks at the spot heated by surface tension, thus forming small cavitations or pores. As a result, light can pass through these cavitations and is reduced to a constant density Dmin value, which depends on the laser energy applied.

[0005] According to EP 0 384 041, a method for producing a heat mode recording material having the possibility of direct read actor write (DRAW) with a thin metal layer, preferably a bismuth layer, for heat mode recording on a web support is provided. Provided and characterized in that, in the same vacuum environment, a protective organic resin layer in the form of a web is laminated to the recording layer supported by an adhesive layer.

[0006] According to EP 0 678 569, which describes a further improvement over the teachings of EP 0 384 041, a direct read-after-write (DRA)
W) a method for producing a heat mode recording material having a capability and comprising a heat mode recording metal layer on a permanent support, comprising: (1) a layer or layer combination comprising 20 μm
Forming a laminated web by laminating a single adhesive layer or a multilayer combination carried by a web-type temporary support having the following thickness to the recording layer under heat and pressure; and Separating the temporary support from the adhesive layer and leaving the single adhesive layer as a protective element on the recording layer, or (2 ') separating the temporary support from the adhesive layer combination Leaving the layer combination as a protective element on the recording layer, and (3) the separating step (2).
Or (2 ') afterwards, comprising a continuous step of chemically curing said single adhesive layer or said outermost layer of said multilayer combination by heat and / or ultraviolet or electron beam radiation. In this embodiment, the single adhesive layer or combination must have a minimum thickness of 5 μm.

In the latter document, a metal layer, preferably a bismuth layer, is applied by vacuum evaporation to a permanent support, preferably a PET support, before lamination of the pack of adhesive layer and temporary support. As a result, the metal layer / permanent support interface is smooth and has a glossy appearance, as opposed to
The upper side of the metal layer, which is later laminated with a thin adhesive layer pack, has a rather rough and dark appearance. With this material, design laser recording through either side of the material creates problems. From the point of visual activation, recording through a thin layer pack on the dark side of the bismuth layer is most advantageous because it is the least reflective side. However, the inherent thickness variations in thin adhesive layer packs create strong interference patterns. On the other hand, exposure through the permanent support side (shiny side) is energetically disadvantageous due to high reflection.

The present invention constitutes an improvement over the teachings of EP 0 678 569.

It is an object of the present invention to have improved sensitivity,
It is an object of the present invention to provide a method for producing a heat mode recording material based on a thin metal layer.

Another object of the present invention is to provide a method for obtaining a heat mode image by laser exposure of such a thin metal layer recording material which is hardly noticeable to the generation of an interfering interface pattern.

Yet another object of the present invention is to obtain a heat mode image which can be used as a master for exposure of printing plates or graphic arts contact films based on silver halide chemistry or as a master for PCB applications. The purpose is to provide a method.

SUMMARY OF THE INVENTION The object of the present invention is to provide (A) the following layers in the following order: (1.1) temporary support, (1.2) release layer, (1.3) protective layer, 1.4) optional intermediate layer, (1.5) undercoat layer,
(1.6) a layer pack (1) comprising a thin metal layer, comprising the following layers: (2.1) a pressure-sensitive adhesive or a heat-adhesive layer, (2.2) a layer pack comprising a permanent transparent support ( 2), the thin metal layer (1.6) and the pressure-sensitive adhesive or thermal adhesive layer (2.
(B) the temporary support (1.1) and the release layer (1.
This is realized by providing a method for producing a heat mode recording material, which comprises the step of removing the 2) by a peeling method, and thus obtaining a heat mode recording material.

The heat mode image can be obtained by exposing the heat mode recording material as described above to intense laser radiation according to the information, preferably with an infrared laser.

In this case, since there is a thin layer pack on the other side which is susceptible to thickness fluctuation, no interference pattern is generated,
The heat mode material can be exposed through a permanent support on the dark bismuth side which is energetically favorable.

[0015] In a preferred embodiment, the thin metal layer is a bismuth layer.

In another embodiment of the invention, the protective layer is based on a radiation-curable composition as described in EP 0 687 569, in which case an optional intermediate layer (1.3) and a subbing layer (1.3). 1.5) can be omitted.

DETAILED DESCRIPTION OF THE INVENTION Transparent organic resin supports useful for the permanent support (2.2) and the temporary support (1.1) include, for example, cellulose nitrate films, cellulose acetate films, polyvinyl acetal films , Polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, or poly-
Includes α-olefin films such as polyethylene or polypropylene films. In the most preferred embodiment of the present invention, both the permanent and temporary supports are polyethylene terephthalate supports with or without a subbing layer. Another suitable support is so-called syndiotactic polystyrene, since this resin exhibits excellent dimensional stability under conditions of temperature and relative humidity fluctuations. The use of such supports for photographic films has already been described in EP 0 423 712 and EP 0 677 778. This support is described in EP03840 described above.
It is also very suitable for the embodiments described in No. 41 and EP 0 678 569.

The thickness of the temporary support is preferably comprised between 10 and 200 μm. The thickness of the permanent support is 75-175
It is preferably in the range of μm.

The release layer can be based on various compositions. The PET support may be prepared, for example, using co (vinylidene chloride-
Methyl methacrylate-itaconic acid: 88/10/2)
And when primed with a layer containing KIESELSOL 100F, the release layer is made of colloidal silica such as KIESE
Preferably, it is based on a combination of LSOL 300F and LAPONITE S, for example in a ratio of 75/25. Alternatively, the release layer can be based on polyvinyl alcohol. Such a polyvinyl alcohol-based release layer can be pre-cured by, for example, crosslinking with tetramethoxysilane. In contrast, when the polyethylene terephthalate or cellulose triacetate support is not primed, the release layer can contain co (vinyl acetate-crotonic acid; 95/5), or it can be a silicone layer, or Polyhydroxystyrene and T as marketed by Maruzen Co.
It can also be based on a combination of polyamides such as AMILAN CM8000 from oray Co. The thickness of the release layer is preferably in the range of 0.3 to 5 μm.

The composition of the protective layer is, in a preferred embodiment, based on nitrocellulose. However, other possible main polymer components include polymethyl methacrylate, such as ACRYLOID K120N (Rohm and Haas C
o.) or ELVACITE 2010 (DuPont Co.),
Polyethyl acrylate such as ELVACITE 204
3 or 2045 (DuPont Co.), CARBOSET
526 (Goodrich), co (vinylidene chloride-vinyl acetate) such as UCAR VYNS-3 (Union
Carbide Co.), or DYNAPOL L912 or L206 (Huels Troisdorf AG).

On the other hand, the protective layer is made of the above-mentioned EP 06875.
It may be based on a radiation-curable composition, as described at 69 for the adhesive layer or layer combination.
As described therein, such radiation-curable compositions comprise as major components: (1) at least one reactive (pre) polymer or oligomer, (2) optionally at least one which dissolves (1). And (3) a photoinitiator in the case of UV curable formulations.

In the composition (1), the reactive (pre) polymer or oligomer includes a compound containing one or more ethylenically unsaturated groups. Reactive polymers containing ethylenically unsaturated groups are commercially available from BOMAR Specialties Company under the trade name JAYLINK (modified cellulose polymer containing acrylamidomethyl groups).

These reactive (pre) polymers or oligomers (1) are preferably present in the composition in an amount of 10 to 1
And the reactive solvent is present in a 0 to 10% by weight ratio.

The photoinitiators having UV-absorbing power when present are used in the lowest possible concentration, for example in a concentration of 0.1 to 1% by weight, based on the total coating composition. Preferably, a photobleachable photoinitiator is used.

Examples of suitable prepolymers for use in the radiation-curable composition of the applied protective layer include unsaturated polyesters such as polyester acrylates; urethane-modified unsaturated polyesters such as urethane-polyester-acrylates. Liquid polyesters having an acrylic group as a terminal group, for example, saturated copolyesters having an acrylic type terminal group are disclosed in published EP-A0207.
257 and Radiat. Phys. Chem., Vol. 33, No. 5, pp. 443-450 (1989).

Copolyesters which are substantially free of low molecular weight unsaturated monomers and other volatiles are of very low toxicity (see periodicals Adhaesion 1990,
Heft 12, page 12). The production of a very wide variety of radiation-curable acrylic polyesters is described in German published patent no.
2838691. 2 of the prepolymer
Mixtures of more than one species may be used.

Other polymers suitable for use in radiation (ultraviolet or electron beam) curable compositions are described, for example, in PK SITA Technology (1991), London, PK
T. OLDRING, Chemistry & Technology of UV
and EB formulation forcoating, inks and pai
nts Vol.2: Prepolymers and Reactive diluents
It is selected from the group consisting of unsaturated urethane (meth) acrylates, epoxy (meth) acrylates, polyether (meth) acrylates and polyester (meth) acrylates as described in for UV and EB curable formulations. A survey of UV-curable coating compositions is described, for example, in the periodical Coating 9/88, pages 348-353.

[0028] Other UV-curable layers can be obtained by the use of prepolymers, also called oligomers of the aliphatic and aromatic polyester-urethane acrylate group. The structure of polyester urethane acrylate is based on the Federation of Societies for 1315 on Wolnut Street, Philadelphia, PA, USA
Published by Coatings Technology (June 1986), Joh
n R. Constanza, AP Silveri, and Joseph A. V
ona, page 9 of Radiation Cured Coatings.

The chemical structure of a particularly useful aromatic polyester-urethane acrylate prepolymer is represented by the following general formula:

[0030]

Embedded image

Examples of the preparation of aliphatic polyester-urethane acrylates are described in US Pat. No. 4,983,505 and DE 2
530896.

For one polymer chain of the prepolymer, the introduction of a large number of acrylic double bonds is carried out by first partially esterifying a polyol, for example, pentaerythritol with acrylic acid, and then increasing the polyol still free HO groups. It is carried out by reaction with a functional isocyanate.

The group I group of UV-cured pressure-sensitive adhesives which are suitable for use according to the invention in pressure-sensitive curable layer compositions,
There are acrylate-grafted polyvinyl alkyl ethers and monoacrylate-grafted polyethers of the group II, Journal of Radiation Curing, Vol.
/ No. 2 (April 1982).

The UV or EB curable coating composition may contain an inert polymer, which does not crosslink,
By their inherent hardness are meant polymers which counteract the scratch resistance of the protective layer and the sticking to the back side of the recording material when rolled up. For this purpose, for example, polyesters derived from aromatic acids such as iso- or terephthalic acid, C1
-C4 alcohol poly (meth) acrylates such as n
-Butyl methacrylate, and their copolymers with styrene and polyvinyl acetate.

When the adhesion between layers (1.3) and (1.5) is not ideal, an intermediate layer can be used. In a preferred example, this optional intermediate layer contains a combination of nitrocellulose, gelatin and maleic acid, and is coated from a solvent mixture such as methanol / acetone / water. In another, but slightly less preferred, example, the nitrocellulose is omitted from the coating mixture.

A good undercoat layer, which affects the distribution and shape of the molten metal droplets in the exposed areas, must be ensured for good adhesion to the thin metal layer to be applied thereon,
Preferably, it is based on one of the following main components:

(1) Copolyester, DYNAPOL L
912 (Huels AG); (2) Ko (vinyl acetate-vinyl alcohol-vinyl acetal), such as S LEC (Sekisui Co.); (3) Polyamide, such as AMILAN CM8000.
(4) 2-hydroxyethyl ether, such as EHEC ext
ra low or EHEC high (Hercules Co.); (5) Ko (styrene-acrylonitrile), for example LUR
AN 388S NATUR (BASF AG); (6) co (styrene-butadiene) such as KRO3 (Ph
(7) Ko (styrene-butyl methacrylate), such as T
ONERHARZ VPOT 5603 (Degussa C
o.); (8) NEOCRYL GL30AC (Polyvinyl Chemi
e); (9) Ko (vinyl acetate-crotonic acid), such as MO
WILITH CT5 (Hoechst); (10) Styrene, for example SUPRAPAL LG840
4 and LR8404 (BASF AG).

The most preferred embodiment is the introduction of a polymeric linear copolyester such as DYNAPOLL912 type.

Possible metals for the recording layer in the present invention include Mg, Sc, Y, Ti, Zr, Hf, V, Nb,
Ta, Cr, Mo, W, Mn, Re, Fe, Co, N
i, Ru, Rh, Pd, Ir, Pt, Cu, Ag, A
u, Zn, Cd, Al, Ga, In, Si, Ge, S
n, As, Sb, Bi, Se, and Te. These metals can be used alone or as a mixture or alloy of at least two of them. Due to their low melting points, Mg, Zn, In, Sn, Bi and Te
Is preferred. The most preferred metal for the practice of the present invention is B
i.

A metal recording layer was formed on the undercoat layer (1.5).
It can be applied by vapor deposition, sputtering, ion plating, chemical vapor deposition, electrolytic plating, or electroless plating. In the preferred case of Bi, the recording layer is preferably applied by vacuum evaporation. Such a deposition method and apparatus is described in the aforementioned EP 0384401.

The thickness of this Bi layer is preferably comprised between 0.1 and 0.6 μm. If this thickness is too small, the recorded image will not have sufficient density. On the other hand, when the thickness is too large, the sensitivity tends to decrease, and the minimum density, that is, the density after laser recording in the exposed area tends to increase.

The composition of the (hot) adhesive layer of the layer pack 2 is as follows:
Preferably based on one of the following components:

(1) Ko (vinyl acetate-ethylene-vinylidene chloride), VINNAPAS dispersion CE
F19 (Wacker Chemie); (2) co (acrylate-methyl acrylate-styrene), such as SYNTACRYL VSW6899; (3) polyurethane resin, such as PT19 (Bayer AG
(4) acrylate copolymers, such as PRIMAL AC
1561 (Rohm and Haas Co.); (5) Methacrylate copolymer, for example, PLEXTOL
M718 or PLEXTOL M600 (Roehm GMBH
(6) co (ethyl acrylate-methyl methacrylate), such as PLEXIGUM MB319 (Rohm an)
d Haas Co.); (7) poly (vinyl acetate), such as DARATAC
61L (WR Grace & Co.) Or GELVA V80
0 (Monsanto Co.); (8) Ko (methyl methacrylate-ethyl acrylate)
X), such as CARBOSET 514A (Goodrich
(9) Ko (styrene-acrylate), such as UCECR
YL 812B (UCBS.A.); (10) Poly (urethane ester), for example DISPER
(11) Ko (styrene-butadiene-acrylic acid), such as BAYSTAL P2005 (Bayer AG); (12) Poly (acrylate), such as ACRYSOL.
WS68 (Rohm and Haas Co.); (13) Ko (vinyl acetate-vinyl laurate), such as 25 VL (Wacker Chemie); (14) Ko (styrene-butadiene), such as PLIOL
ITE S5B (Goodyear Co.); (15) Ko (vinyl acetate-crotonic acid), for example, M
(16) Ko (vinyl acetate-vinyl laurate-crotonic acid), for example, VINNAPAS B100 (Wacker)
(17) copolyesters such as DYNAPOLL L4
11 or S1420 (Huels AG).

In a preferred embodiment, the adhesive layer is a co (styrene-acrylate) such as UCECRYL 8
Contains 12B (UCB SA).

At room temperature, a weak pressure-sensitive adhesive is applied to the adhesive layer (2.
It will be readily appreciated that when 1) is included, the layer pack (2) must itself be provided with a temporary cover sheet and a release layer, otherwise the combination cannot be rolled up. . Immediately before lamination, the temporary cover sheet and the release layer are removed by peeling. In another implementation, a silicone layer is provided on the back side of the permanent support, but without the cover sheet. This combination can be rolled up and unwound because the silicone layer has an adhesive effect on the adhesive layer.

Lamination of the layer pack (2) onto the layer pack (1) places the two materials in contact and then introduces these materials under suitable pressure into the nip of a pair of heated laminating rollers. Can be done by Suitable lamination temperatures usually range from about 10 ° C to 100 ° C, preferably 20 ° C.
C. to 50.degree. The lamination step can be performed offline, but more preferably performed online.
This means that it takes place in a vacuum chamber immediately after the application of a thin metal layer, preferably bismuth, by vacuum deposition. With this method of handling, the layer pack (1) does not have to be rolled up before laminating it with the layer pack (2), and possible physical damage of the metal layer is avoided.

The method of peeling the temporary support and the peeling layer can be carried out by hand or with a layer peeling device. At that time, the delamination can be performed off-line, but in a preferred case where the lamination is performed online, the delamination can still be performed online in a vacuum chamber. Finally, the finished heat mode material is wound up and stored.

As detailed above and in the sense of EP 0 678 569, when the protective layer is based on a photocurable composition, it can be carried out at various stages of the following process:

(1) Before the lamination of the layer pack (2), after the coating of the protective layer; (2) After the lamination but before the delamination; (3) After the delamination of the temporary support and the release layer.

When the protective layer is based on a radiation-curable composition, there is another particularly simple embodiment for the method according to the invention. Simply remove layers (1.4) and (1.5). In this case, the method comprises: (A ') the following layers in the following order: (1'.1') temporary support, (1'.2 ') release layer,
(1'.3 ') a radiation-curable protective layer, (1'.4') a layer pack (1 ') comprising a thin metal layer, with the following layers: (2'.1') pressure sensitive adhesive or heat Adhesive layer, (2 ′.
2 ') Laminating on a layer pack (2') containing a permanent transparent support, the thin metal layer (1'.4 ') and the pressure-sensitive adhesive (2'.1') or heat adhesive layer Face to face,
(B ′) The temporary support (1′.1 ′) and the release layer (1′.2 ′) are removed by a peeling method, and (C ′) before or after the laminating step (A ′). There is a peeling step (B ')
Before or after peeling, curing the protective layer (1'.3 ') by radiation, thus obtaining a heat mode recording material.

Successful implementation of this particular embodiment requires that the protective layer before and after curing show good adhesion to thin metal layers and allow good distribution of metal particles after laser recording. I do. In other words, the curable protective layer (1'.3 ') must combine the required good properties of the original protective layer (1.3) and the subbing layer (1.5).

After removing the temporary support and the release layer by delamination, the obtained heat mode material is subjected to exposure according to laser information. It is essential that this exposure be done through the back of the transparent permanent support. In a preferred embodiment, the intense laser radiation is produced by an infrared laser. Particularly preferred lasers are semiconductor diode lasers or solid state lasers such as 1064 nm
Nd-YAG laser emitting at 1053 nm or Nd-YLF laser emitting at 1053 nm. Other possible infrared laser types include diode lasers. Important parameters of laser recording are spot diameter (D) measured at 1 / e ^{2 of} intensity, applied laser power on film (P), laser beam recording speed (v) and points per inch. (Dpi).

The presence of heterogeneous regions in the thermal adhesive layer coated as an aqueous polymer latex can cause bubbles during laser recording. However, this can be improved by vigorous rubbing after recording or by applying high mechanical pressure.

The following examples illustrate, but do not limit, the invention.

EXAMPLE Production of a one- layer pack 1 having a thickness of 100 μm and containing 75% by weight of co (vinylylene chloride-methyl acrylate-itaconic acid (88/1)
0/2) and 25% by weight colloidal silica KIISE
A KIESEL having a thickness of 0.25 μm on a polyethylene terephthalate (PET) temporary support provided with a subbing layer containing LSOL 100F (registered trademark of Bayer AG)
SOL 300F (registered trademark of Bayer AG) (75%)
And a release layer consisting of LAPONITE S (registered trademark of Laporte Co.) (25%).

On this release layer, the following coating solution was applied, and after drying, a protective layer having a thickness of 3 μm was obtained.

Nitrocellulose (DS: 2.25) ^* 26 g methanol 335 ml ethanol 365 ml diethyl ether 250 ml n-propanol 50 ml * indicates the degree of substitution.

On this protective layer, the following coating solution was applied so as to obtain a 1 μm thick intermediate layer after drying:

Water 30 ml Gelatin 12 g Maleic acid 1 g Butanol 200 ml Methyl ethyl ketone 370 ml Ethanol 400 ml Nitrocellulose (DS: 2.25) 7.5 g

A sample of this pack was provided with an undercoat layer I.A. provided a:

I. a Water 36 ml Gelatin 1.25 g Maleic anhydride 0.125 g ZELEC NK (DuPont) (fluorosurfactant) 5 mg Methanol 5 ml Acetone 25 ml Formol (40%) 0.05 ml The volume was adjusted to 125 ml with water.

Four other subbing layer coating compositions (I.b.
I. e) was applied to the samples of the layer pack, however, in these cases the intermediate layer was omitted. Thus, the subbing layer was coated directly on the protective layer.

I. b Toluene 66g Ethyl acetate 29g Polystyrene (SUPRAPAL LG8404-BASF) 5g

I. c 65 g of ethanol 30 g of methanol 5 g of polyamide (AMILAN CM8000-Toray)

I. d Toluene 66 g Ethyl acetate 29 g Copolyester (DYNAPOL L912-Huels) 5 g

I. e Toluene 66 g Ethyl acetate 29 g Co (vinyl acetate-vinyl alcohol-vinyl acetal) 5 g

All of these subbing layer compositions were dried to a thickness of 1
μm.

Finally, for each of the layer packs, LE
300n on the undercoat layer side by vacuum evaporation (10 ^-3 mbar) with a YBOLD-HERAEUS type 1140 device
A m-thick bismuth layer was applied.

Preparation of Layer Pack 2 (vinylidene-methyl acrylate-itaconic acid)
(88/10/2) 75% and KIESELSOL 1
The following thermal adhesive composition was coated on a 100 μm thick polyethylene terephthalate support provided with a subbing layer containing 00F (Bayer AG) (25%): 18.18 ml of UCECRYL 812B (55%) (UCB SA)
Was diluted to 100 ml with water and coated to a dry thickness of 5 μm.

[0070] In the conveying speed of the laminating step 100 cm / min and 65 to 70 ° C., COD
OR LPP650 Laminating Machine (Dorned BV, The Ne
The layer pack 2 was laminated on each sample of the layer pack 1 at therlands.

Finally, the temporary support and the release layer of each layer pack 1 were peeled off.

Laser recording The resulting heat mode recording material was imagewise exposed through a permanent support with a NdYLF laser having the following recording parameters. (1) Pitch: 2117 dpi (all areas), 200 dpi
i (single scan line); (2) recording speed 4.4 m / s; (3) power on film: 0.52 watts; (4) spot diameter (1 / e ² ): 14.9 μm.

Table 1 summarizes the results.

Table 1 Quality Quality sample No. Dmax Dmin Sensitivity ^* Single scan line Bi distribution Ia 3.6 0.22 5.0 × 10 ⁶ Slightly cut Very fine Ib 4.5 0.20 5.6 × 10 ⁶ Slightly cut Very fine Ic 4.65 0.19 4.0 × 10 ⁶ little cut Fine Id 4.6 0.19 3.6 × 10 ⁶ no cut Fine Ie 4.0 0.21 5.0 × 10 ⁶ Very little Very fine * Sensitivity expressed in mJ / m ² : If the number is small, The smaller the value, the higher the sensitivity.

In any of the above cases, no disturbing interference patterns occurred.

Example 2 In this example, on the other hand, the prior art EP 06875
The physical properties of the heat mode bismuth recording material designed according to the 69 principle (Comparative Material I) and the heat mode bismuth recording material designed according to the present invention (material II of the present invention) were compared. The main features of both materials were as follows (Table 2)
a):

Table 2a Material I Material II layer pack 1 layer pack 1 (1) Same as PET 100 μm I (2) 75% co (ViCl ₂ -MA-IA) ^* (88/10/2) / 25% KIESELSOL 100F (Bayer) Same as 0.1 μm thickness I (3) Release layer: KIESELSOL 300F / LAPNITE S (Laporte) (75/25) Same as 0.25 μm thickness I (4) Protective layer: nitrocellulose 3 μm thickness I (5) Intermediate layer: nitrocellulose / gelatin (see Example 1) Same as I (6) Adhesive layer: UCECRYL 812B Undercoat layer: 75% co (ViCl ₂ -MA-IA) 5 μm thick (88 / 10/2) / 25% KIESELSOL 100F Bi layer material deposited on the undercoat layer Material I Material II layer pack 2 layer pack 2 (1) Bi layer deposited on the undercoat layer (2) Undercoat layer: 75 % Co (ViCl ₂ -MA-IA) (88/10/2) Adhesive layer: UCECRYL 812B / 25% KIESELSOL 100F, thickness 1 μm, thickness 5 μm (3) 75% co (ViCl ₂ -MA-IA) ( 88/10/2) / 25% KIESELSOL 100F, same as thickness 0.1 μm I (4) Same as PET 100 μm I *: Co (vinylidene chloride-methyl acrylate-itaconic acid)

Table 2b compares the properties of the two materials.

Table 2b Characteristic material I Material II Dmax 3.5 3.8 Dmin 0.20 0.23 Sensitivity ^* 6.1 × 10 ⁶ mJ / m ² 4.2 × 10 ⁶ mJ / m ² AgX recording film Compatibility ^** good Very good Exposure latitude << AgX film <AgX film Thickness of protective laminate 9 μm 5 μm Recording side Gloss side Dark side *: Condition: spot diameter NdYLF laser (1 / e ² ) = 15 μm V = 4.4 m / s **: Copied and tested on AgX contact material and on printing plates sensitized before positive and negative action.

From Table 2b, the advantage of the recording material according to the invention is that a thinner protective laminate on the Bi layer and a higher sensitivity are evident. Exposure on the energetically favorable dark bismuth side is possible without the occurrence of interference patterns. The compatibility with the AgX film is improved. In the case of the comparative material, exposure on the energetically disadvantageous smooth bismuth side is necessary to avoid these interference patterns.

Example 3 In the above example, the layer packs 1 and 2 were laminated on each other by separate thermal laminating machines. In doing this, care must be taken not to damage the physically vulnerable bismuth layer. In the present embodiment, the laminating step
Prove that the same material properties are obtained when performed online in a vacuum chamber.

Sample I of Example 1 The production of d was repeated until the coating of the subbing layer (layer 1.5). A 1200 W infrared emission source was mounted in the Heraeus vacuum chamber at a distance of about 80 cm from the application area of the bismuth layer and about 3 cm from layer pack 1. The layer pack 2 was stacked further about 5 cm apart from the layer pack 1 preheated by a pair of laminating rollers. The temporary support was peeled off-line.

In Example 1 I. The same characteristics as in d were obtained.
However, a major advantage was that a completely scratch-free and pinhole-free recording material could be made by the on-line method.

Example 4 In this example, the protective layer (1.3) was a photocurable layer.

The following layer pack was made:

Layer Pack 1: (1) Temporary support; PET 100 μm having the following undercoat layer
m: (a) 75% co (ViCl ₂ -MA-IA) (88/10
/ 2) / 25% KIESELSOL 100F (Bayer
), 0.1 μm thick, and (b) 80% gelatin and 2
0% KIESELSOL 100F, thickness 1 μm; (2) undercoat layer; polyvinyl alcohol (POLYVIOL)
V03, Wacker Chemie), 1 μm thick, coated from a 5% aqueous solution containing 0.2% of the commercial wetting agent ULTRAVON; (3) Photocurable protective layer coated from the following composition: HABI (1,1 '-Biimidazole-2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl) 1.5 g mercaptobenzoxazole 0.08 g Michler's ketone 0.12 g co (styrene-acrylate) ( Tonerharz
VPOT5152 (Degussa) 9.8 g dipentaerythritol pentaacrylate (SR39
9, SARTOMER) 7.2 g Methyl ethyl ketone 181.3 g

The composition was coated with a 40 μm coating knife to a dry thickness of about 3.4 μm. 30 by vacuum evaporation
A 0 nm thick bismuth layer was applied (see Example 1).

Layer pack 2 was the same as one of Example 1.

The two layer packs were laminated together on a CODOR LPP650 laminator at 65 ° C. at a transport speed of 100 cm / min. Curing of the protective layer was performed by ultraviolet radiation in the following manner. UV contact exposure device CDL1501
(Agfa Gevaert NV), the finished assembly was uniformly exposed for 30 seconds at a power of 2300 μW / cm ² through a transparent support. After this light curing, the temporary support was peeled off. Laser recording was performed in the same manner as in Example 1. The following results were obtained (Table 3):

Table 3 Sensitivity 5.1 × 10 ⁶ mJ / m ² Dmin 0.21 Dmax 4.32 Single scan line quality No abrasion Bi distribution Fine good quality Scratch resistance Very good

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Stevan Lezi Morseur, Belgium, Septetriat 27 Agfa Geverth na Mroseze Bennoutchap (72) Inventor Joan Ramot, Morteseale, Belgium Septetrat 27 Inside Agfa Geverth na Mroseze Bennoutchap (72) Inventor Luc Landel Septetraat, Morzère, Belgium 27 Inside Agfa Gewertner Mlose Bennoutchap (56) References JP-A-2-266799 ( JP, A) JP-A-5-131786 (JP, A) JP-A-7-329425 (JP, A) JP-A-5-51671 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , (DB name) B41M 5/26 B41M 5/36

Claims (18)

(57) [Claims] 1. (A) The following layers in the following order: (1.1) Temporary support, (1.2) Release layer, (1.3) Protective layer, (1.4) Optional intermediate layer , (1.5) undercoat layer,
(1.6) a layer pack (1) comprising a thin metal layer, comprising the following layers: (2.1) a pressure-sensitive adhesive or a heat-adhesive layer, (2.2) a layer pack comprising a permanent transparent support ( 2), the thin metal layer (1.6) and the pressure-sensitive adhesive or thermal adhesive layer (2.
(B) the temporary support (1.1)
And a step of removing the release layer (1.2) by a release method, thereby obtaining a heat mode recording material. 2. The method of claim 1, wherein said protective layer comprises nitrocellulose. 3. The protective layer contains a radiation-curable composition and is provided before the laminating step (A), or between the laminating step (A) and the peeling step (B), or in the peeling step (B). 2. The method of claim 1, wherein the curing is performed by radiation. 4. The method according to claim 3, wherein the curing is performed by ultraviolet radiation, an electron beam, or a heating step. 5. The method according to claim 1, wherein the thin metal layer is a bismuth layer. 6. The method according to claim 1, wherein the thin metal layer is applied on the undercoat layer by vacuum evaporation. Method. 7. The method according to claim 1, wherein the intermediate layer (1.4) contains a mixture of nitrocellulose, gelatin and maleic acid. 8. The undercoat layer (1.5) comprises a polymeric linear copolyester.
The method according to any one of the preceding claims. 9. The method according to claim 1, wherein the adhesive layer (2.1) contains a co (styrene-acrylate) copolymer. 10. (A ') the following layers in the following order: (1'.1') temporary support, (1'.2 ') release layer,
(1'.3 ') a radiation-curable protective layer, (1'.4') a layer pack (1 ') comprising a thin metal layer, with the following layers: (2'.1') pressure sensitive adhesive or heat Adhesive layer, (2 ′.
2 ') Laminating on a layer pack (2') containing a permanent transparent support, the thin metal layer (1'.4 ') and the pressure-sensitive or heat-sensitive adhesive layer (2'.1') are interconnected. Face to face,
(B ′) The temporary support (1′.1 ′) and the release layer (1′.2 ′) are removed by a release method, and (C ′) before the lamination step (A ′) or in the lamination step Curing the protective layer (1'.3 ') with radiation between (A') and the stripping step (B ') or after the stripping step (B'), and thus the heat mode recording material A method for producing a heat mode recording material, comprising: 11. The method according to claim 10, wherein the curing is performed by ultraviolet radiation, an electron beam, or a heating step. 12. The radiation-curable protective layer (1 ′.
12. The method according to claim 10, wherein 3 ') comprises a multifunctional acrylate monomer. 13. The method according to claim 10, wherein the thin metal layer is a bismuth layer. 14. The method according to claim 10, wherein the curable adhesive layer (2′.1 ′) contains a co (styrene-acrylate) copolymer. 15. The radiation-curable adhesive layer (1′.3 ′) formed by vacuum deposition of the thin metal layer (1′.4 ′).
15. The method according to any one of claims 10 to 14, wherein the method is applied above. 16. The heat mode recording material as defined in claim 1, which is exposed to intense laser radiation through the back side of said permanent transparent support (2.2) or (2′.2 ′). A method for forming a heat mode image, comprising exposing according to information. 17. The method of claim 16, wherein said intense laser radiation is produced by an infrared laser. 18. The method of claim 17, wherein said infrared laser is a solid state laser or a semiconductor diode laser.